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CN101432326A - Segmented polyurethane elastomers with high elongation at tear - Google Patents

Segmented polyurethane elastomers with high elongation at tear Download PDF

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Publication number
CN101432326A
CN101432326A CNA2007800148030A CN200780014803A CN101432326A CN 101432326 A CN101432326 A CN 101432326A CN A2007800148030 A CNA2007800148030 A CN A2007800148030A CN 200780014803 A CN200780014803 A CN 200780014803A CN 101432326 A CN101432326 A CN 101432326A
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CN
China
Prior art keywords
isocyanate
fiber
prepolymer
polyurethane
end capped
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Pending
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CNA2007800148030A
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Chinese (zh)
Inventor
D·罗德瓦尔德
H·格拉夫
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BASF SE
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BASF SE
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Publication of CN101432326A publication Critical patent/CN101432326A/en
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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The current invention relates to a process for the manufacture of a polyurethane elastomer fiber in which a) a polymer diol and a substance that reacts to a polymer diol are converted to an OH-terminated prepolymer; b) the OH-terminated prepolymer with one diisocyanate is converted to an isocyanate-terminated prepolymer; c) the isocyanate-terminated prepolymer with one chain extension, possibly one chain stopper, and possibly additional additives, is converted to a polyurethane elastomer; and d) the polyurethane elastomer is spun to a fiber whereby less than 15% by weight of additional polyurethane elastomers are contained in the fiber. The current invention furthermore relates to a polyurethane elastomer fiber obtained using a process of this type used to manufacture textiles, such as for example, woven or knitted, as well as the use of a polyurethane elastomer for the manufacture of such a fiber.

Description

Segmented polyurethane elastomers with high elongation at tear
The present invention relates to a kind of method of producing polyurethane elastomeric fiber, comprise and a) make polymer diol and it is the end capped prepolymer of reactive substance reaction formation OH, b) make end capped prepolymer of this OH and di-isocyanate reaction form isocyanate-terminated prepolymer, c) make this isocyanate-terminated prepolymer and chainextender, suitable words chain terminator and suitable other additive reactions of words form polyurethane elastomers, and d) this elastomerics spinning is formed fiber, wherein in this fiber, have other polyurethane elastomers less than 15 weight %.
The invention further relates to a kind of polyurethane elastomeric fiber that can obtain by this method, its purposes and polyurethane elastomer purposes in producing this fiber in producing textiles such as woven or knitted fabrics.
Other embodiments of the present invention can be understood by claims, specification sheets and embodiment.The feature that is understood that the above-mentioned of theme of the present invention and hereinafter still will describes in detail not only can with shown in the particular combinations utilization, and can utilize with other combinations that do not deviate from the scope of the invention.
By at least 85% elastic polyurethane fiber of forming based on for example segmented polyurethane of polyethers, polyester and/or polycarbonate is well-known.Be used to produce textiles by such fibrous yarn, as fabric, the latter can be used for foundation garment, stocking and Sportswear especially again, and example is bathing gown and swimming trunks.The segmented polyurethane fiber is to comprise second-order transition temperature to be lower than 0 ℃, preferably is lower than-30 ℃ the soft chain segment and the fiber of crystallinity hard segment.
Elastic polyurethane fiber, especially puu fiber have excellent elasticity and significant extensibility and high reservation power.Because this excellent performance combination, they are widely used in the garment industry.Such elastic polyurethane fiber and production method thereof for example are described among US 5541280, US 6692828, EP1401946, DE 19931255, JP 63-219620 and the US 6503996.
The shortcoming of these elastic polyurethane fibers comprises elongation at break deficiency in some applications, and this only allows to mix in the textiles under low preliminary draft conversely; Wear at 200-400% common that tension force still significantly increases under the elongation of field, especially this it is may cause uncomfortable constriction under the high resilience polyurethane fibre content, for example as at medical bandage or support in the textiles and under the closing in situation on for example socks or the baby diaper, and compare disadvantageous hysteresis behavior with for example rubber yarn.
For example tension force substantially constant in wide elongation scope is an ideal in a lot of the application.The textiles that comprises this fibrid produces substantially invariable pressure to the health of wearer, and is irrelevant with the elongation of dressing the district.This is a particularly important for the fabric that for example is used for medical bandage or for example being used under the closing in situation of baby diaper.Has the rubber fibre of more flat elasticity platform equally because its easy oxidation, to be difficult to make low linear density and to bring out latex potentiality hypersensitive also be disadvantageous.
These shortcomings can not occur when the multipolymer with tetrahydrofuran (THF) and 3-methyltetrahydrofuran is used to produce polyurethane elastomeric fiber.This fibrid for example is described among US 5000899 and the EP 1240229.But the availability that a shortcoming of these fibers is 3-methyltetrahydrofurans is poor.
The purpose of this invention is to provide a kind of performance characteristic, especially elongation at break, elasticity platform and stress-strain behavior be to similar with the fiber of the multipolymer of 3-methyltetrahydrofuran based on tetrahydrofuran (THF), but do not require the polyurethane elastomeric fiber that any 3-methyltetrahydrofuran is produced.
We find that this purpose is realized by the method according to claim 1, this method comprises a) to be made polymer diol and it is the end capped prepolymer of reactive substance reaction formation OH, b) make end capped prepolymer of this OH and di-isocyanate reaction form isocyanate-terminated prepolymer, c) make this isocyanate-terminated prepolymer and chainextender, other additive reactions of suitable words chain terminator and suitable words form polyurethane elastomer, and d) this elastomerics spinning is formed fiber to produce polyurethane elastomeric fiber, wherein in this fiber, have other polyurethane elastomers less than 15 weight %.This purpose further can be realized according to the fiber that this method obtains by a kind of.
The adding of other polyurethane elastomers in fiber brought and made this fibre property, and especially it extends the risk of degradation, and this depends on the ratio of other polyurethane elastomers.At this background, comprise less than 15 weight % according to fiber of the present invention, preferably less than 10 weight %, be more preferably less than 5 weight %, particularly other polyurethane elastomers of 0 weight %.
The polymer diol useful to the object of the invention comprises Aethoxy Sklerol, polyesterols or polycaprolactone, the polyethers and the copolyether that for example comprise polytetrahydrofuran and derivative thereof, as polytetrahydrofuran diol, poly-(tetrahydrofuran (THF)-co-Vinyl Ether) glycol, polycarbonate diol, as poly-(carbonic acid 1,5-pentylidene ester) two pure and mild poly-(carbonic acid 1,6-hexylidene ester) glycol and poly-(the inferior propyl ester of ethene-co-hexanodioic acid) two pure and mild polyesterols, as hexanodioic acid, the polyester of butyleneglycol and neopentyl glycol, hexanodioic acid, the polyester of butyleneglycol and hexylene glycol, the polyester of hexanodioic acid and butyleneglycol, the polyester of hexanodioic acid and hexylene glycol, the polyester of the polyester of dodecanedioic acid and neopentyl glycol or sebacic acid and neopentyl glycol.The preferred polycaprolactone that uses, the polyester of hexanodioic acid and butyleneglycol, polytetrahydrofuran diol, the polyester of hexanodioic acid, butyleneglycol and neopentyl glycol, the polyester of hexanodioic acid, butyleneglycol and hexylene glycol, the polyester of hexanodioic acid and hexylene glycol, the polyester of the polyester of dodecanedioic acid and neopentyl glycol or sebacic acid and neopentyl glycol or its mixture.Preferred especially separately or with the mixture of other glycol, use polytetrahydrofuran diol as polymer diol especially separately.
The number-average molecular weight of polymer diol is preferably 200-4000g/mol.When with polytetrahydrofuran diol when the polymer diol, number-average molecular weight is preferably 200-2500g/mol, more preferably 200-2100g/mol, even more preferably 300-1100g/mol, especially 500-800g/mol.
Comprise having the compound that the OH group is reactive group with the material of polymer diol reaction.The OH group is reactive group comprises for example carboxylate group or isocyanate groups, but do not comprise OH group itself at this paper.For example can be the derivative of vulcabond, diacid or diacid with the material of polymer diol reaction.The preferred aromatic substance of using also has aliphatic cpd, as hexamethylene diisocyanate (HDI), and 4,4 '-diisocyanate based dicyclohexyl methyl hydride (HMDI) or isophorone diisocyanate (IPDI).Aromatic substance for example comprises aromatic isocyanate, as 2,2 '-, 2,4 '-and 4,4 '-diphenylmethanediisocyanate, the mixture of various monomer diphenylmethanediisocyanates, 2,4-or 2,6-tolylene diisocyanate (TDI) or its mixture, naphthalene diisocyanate (NDI) or its mixture, aromatic diacid, as terephthalic acid and m-phthalic acid, also has the ester of aromatic diacid, as terephthalate and isophthalic acid ester.Being preferably used as the material that reacts with polymer diol especially is aliphatic ester, especially m-phthalic acid or the dimethyl isophthalate of m-phthalic acid or terephthalic acid and m-phthalic acid and terephthalic acid.
Step a) is more preferably by carrying out the reaction of polytetrahydrofuran diol and m-phthalic acid or dimethyl isophthalate.
Form under the situation that is reflected at isocyanic ester of the end capped prepolymer of OH by polymer diol and isocyanic ester are being preferably 20-120 ℃, more preferably 50-100 ℃, especially mix under 70-90 ℃ the temperature and carry out.Preferred solvent-free the carrying out of this reaction.When using solvent, preferred polar aprotic solvent is as N,N-dimethylacetamide or N, dinethylformamide.Vulcabond is with use in shortage.The OH group is preferably 1:0.8-1:0.5, more preferably 1:0.7-1:0.6 with the ratio of isocyanate groups.This reacts completely when all used isocyanic ester react.This reaction is preferably carried out without catalyzer.When using catalyzer, for example can use phosphoric acid with the concentration of preferred 50-200ppm based on reaction mixture.
When polymer diol being material that reactive material uses as the ester of aromatic diacid or aromatic diacid, this reaction is carried out under esterification or transesterification conditions respectively.Reaction mixture under reduced pressure is heated to for example 150-250 ℃ temperature gradually, and wherein the living product of by-product is removed by distillation.Suitable words can be used as catalyzer with Lewis acid, but preferably do not use catalyzer.When using catalyzer, for example can add boron trifluoride etherate, two lauric acid tin methides, two stannous octoates and tetra-butyl orthotitanate, preferably its concentration is 3-50ppm, especially 5-30ppm.The mol ratio of polymer diol and aromatic diacid or aromatic diacid ester is preferably 1:0.9-1:0.5, more preferably 1:0.9-1:0.6.The number-average molecular weight of the end capped prepolymer of OH is preferably 500-5000g/mol, more preferably 1500-4500g/mol.
The vulcabond that is used to prepare isocyanate-terminated prepolymer in step b) can be any required organic diisocyanate.Preferred vulcabond comprises the linear aliphatic isocyanic ester, as 1,2-ethylidene diisocyanate, trimethylene vulcabond, tetramethylene vulcabond, 1,6-hexylidene diisocyanate, 1,8-inferior octyl diisocyanate, 1,5-diisocyanate based-2,2,4-trimethylpentane, 3-oxo-1,5-pentane vulcabond etc.; Alicyclic diisocyanate, as isophorone diisocyanate, cyclohexyl diisocyanate, preferred 1,4-cyclohexyl diisocyanate, 4,4 '-diisocyanate based dicyclohexyl methyl hydride (HMDI) and aromatic diisocyanate, as 2,2 '-, 2,4 '-and 4,4 '-diphenylmethanediisocyanate, the mixture of various monomer diphenylmethanediisocyanates, 2,4-or 2,6-tolylene diisocyanate (TDI) or its mixture, naphthalene diisocyanate (NDI) or its mixture.Particularly preferred vulcabond is 4, and 4 '-methylenediphenyl diisocyanates (4,4 '-MDI), and 2,4-or 2,6-tolylene diisocyanate, especially 4,4 '-MDI.
Isocyanic ester is with excessive use.The OH group of the preferred end capped prepolymer of OH is 1:1.2-1:3.0 with the ratio of the isocyanate groups of vulcabond, preferred 1:1.3-1:2.0.This reaction is being by being preferably 20-120 ℃ with end capped prepolymer of OH and isocyanic ester, more preferably 50-100 ℃, especially mixes under 70-90 ℃ the temperature and carries out.This reaction is preferably carried out under solvent-free.When using solvent, preferred polar aprotic solvent such as N,N-dimethylacetamide or N, dinethylformamide.The isocyanate content of isocyanate-terminated prepolymer is preferably 0.1-3.75%, more preferably 1-3%.This reaction is preferably carried out under catalyst-free.When using catalyzer, for example can be preferably the concentration use phosphoric acid of 50-200ppm based on reaction mixture.Step b) also utilizes gross weight based on the compound with two isocyanate-reactive groups preferably less than 15 weight % except utilizing the end capped prepolymer of polymerization OH, be more preferably less than 10 weight %, even be more preferably less than 1 weight %, particularly do not use other compounds with two or more isocyanate-reactive groups.
Useful chainextender comprises having two isocyanate reactive hydrogen atoms and the molecular weight compound less than 500g/mol.Such material for example is described in " Kunststoffhandbuch, 7, Polyurethane ", Carl Hanser Verlag, and the 3rd edition, in 1993, the 3.4.3 chapters.For example can use quadrol, 1,2-propylene diamine, 1,3-propylene diamine, 1,4-butanediamine, 1,5-diamino pentane, hydrazine, m-xylene diamine, p dimethylamine, 1,4-cyclohexane diamine, 1,3-cyclohexane diamine, 1,3-diamino-4-methylcyclohexane, 1-amino-3-amino-ethyl-3,5,5-trimethyl-cyclohexane (isophorone diamine), 1,1 '-methylene radical two (4,4 '-diamino hexane), tolylene diamine, piperazine, ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol or its mixture.Preferred especially diamines, as quadrol, 1,2-propylene diamine, 1,3-propylene diamine, 1,4-butanediamine, 1,5-diamino pentane, hydrazine, m-xylene diamine, p dimethylamine, 1,4-cyclohexane diamine, 1,3-cyclohexane diamine, 1,3-diamino-4-methylcyclohexane, 1-amino-3-amino-ethyl-3,5,5-trimethyl-cyclohexane (isophorone diamine), 1,1 '-methylene radical two (4,4 '-diamino hexane) and tolylene diamine and composition thereof, especially quadrol and 1,2-propylene diamine and composition thereof.
Except one or more chainextenders, can also use the isocyanate-reactive compound of chain terminator effect.Useful chain terminator for example comprises secondary amine, as diethylamine, dibutylamine, dicyclohexylamine or primary amine, and as thanomin, or primary alconol, as propyl carbinol, they use separately or as mixture.The preference chain terminator is a monofunctional amines.Except chainextender and chain terminator, can also use special amine, the example is diethylenetriamine or diethanolamine.
When also using chain terminator and/or special amine except chainextender, the ratio of chainextender is preferably 85 weight % or more, and more preferably 90 weight % or more are based on the gross weight of chainextender, chain terminator and special amine.
These chain terminators and special amine can use separately or use with chainextender separately.Preferably separately add chain terminator, special amine and chainextender.Be meant that separately each component can add simultaneously or add at different time with the controlled materials flow of difference.
Primary alconol such as propyl carbinol also can add polymer diol before the end capped prepolymer of this OH of preparation.At this moment, chain terminator and/or special amine can be included in the step c) with chainextender.
Isocyanate-terminated prepolymer preferably carries out in solution to the conversion of polyurethane elastomer of the present invention.Can use polar aprotic solvent.Polar aprotic solvent is the isocyanate-terminated prepolymer of dissolving, but substantially not with the solvent of isocyanate groups reaction.The example of this kind solvent is N,N-dimethylacetamide, N, dinethylformamide, methyl-sulphoxide, N-Methyl pyrrolidone etc.Preferred N,N-dimethylacetamide or the N of using, dinethylformamide especially preferably uses N,N-dimethylacetamide.Preferred in each case will isocyanate-terminated prepolymer, chainextender, suitable words chain terminator and the suitable special amine of words is dissolved in the solvent and also subsequently gained solution mixed mutually.Preferably each solution is separately added in the solution of isocyanate-terminated prepolymer.This can and stream carry out or carry out at different time.In addition, the solution of mixed chain extender, chain terminator and special amine before can be in adding isocyanate-terminated prepolymer.The temperature of reacting is preferably 0-80 ℃, and more preferably 8-50 ℃, especially 10-35 ℃.All isocyanate-reactive materials are usually so that isocyanate-reactive group, and normally amino excessive a little amount is used.Isocyanate groups is preferably 1:1.00-1:1.15 with the ratio of amine groups, more preferably 1:1.00-1:1.04, especially 1:1.00-1:1.02.
Solvent spinning with this complete reaction forms fiber subsequently.Can use any spinning processes that can production fiber of the present invention.Such spinning processes for example is described in " Kunststoffhandbuch, 7, Polyurethane ", Carl Hanser Verlag, and the 3rd edition, in 1993, the 13.2 chapters.These comprise dry-spinning or wet spinning, preferred dry-spinning method.In this spinning processes, the spinning solution that will comprise polyurethane elastomer of the present invention by spinning jet is spun into line.For example by dry or in precipitation bath, remove spin solvent and obtain polyurethane elastomeric fiber of the present invention.
Polyurethane elastomeric fiber of the present invention can further comprise additive.Anyly can use in this article segmented polyurethane elastomers fiber known additives.For example can comprise delustering agent, filler, antioxidant, dyestuff, pigment, dye enhancer, Methacrol 2462 B for example are to the stablizer of heat resistanceheat resistant, light, UV radiation, chlorination water and effect and atmospheric pollution such as the NO or the NO of antagonism flue gas 2Stablizer.Antioxidant and be to be selected from sterically hindered phenol to the example of heat resistanceheat resistant, light or UV radiating stablizer, for example Cyanox 1790, hindered amine as light stabilizer (HALS), triazines, the stablizer of benzophenone and benzotriazole category.The example of pigment and delustering agent is titanium dioxide, Magnesium Stearate, silicone oil, zinc oxide and barium sulfate.The example of dyestuff is matching stain, dispersed dye and pigment and white dyes.Antagonism chlorine or chlorination water are the magnalium hydroxyl carbonates of zinc oxide, magnesium oxide or coating or uncoated to the stablizer example of degradation of fiber, for example hydrotalcite or huntite (huntites).
Polyurethane elastomeric fiber of the present invention has advantageous property on elongation at break, hysteresis behavior and stress-strain behavior.The solution casting polyurethane elastomer film that this favourable behavior used thickness is 0.20-0.26mm characterizes.These films can obtain except that desolvating by spinning solution being poured on the planer surface and by drying.
Elongation at break is the length variations of sample when sample breakage that be stretched, and represents with the % of original length.This measurement is carried out according to ISO 37.Elongation at break according to polyurethane elastomer film of the present invention is preferably greater than 500%, more preferably greater than 600%.
Stress-strain behavior is measured according to ISO 37.Polyurethane elastomer film of the present invention is that stress under 200% elongation is preferably less than 6N/mm at the original length with respect to sample 2, be more preferably less than 5N/mm 2, the stress under 300% elongation is preferably less than 8N/mm 2, be more preferably less than 7N/mm 2, and the stress under 400% elongation is less than 11N/mm 2, be more preferably less than 10N/mm 2
Relative loss (the b of the hysteresis behavior of polyurethane elastomer film of the present invention power during with 5 repeated stretchings W, 5), the hysteresis characteristic (H when the 5th stretches 5) and the tensile stress values (C of the 5th when stretching 5) report.These measurements are carried out according to German standard rules DIN 53825 part 2s.The relative loss of power is represented stretch length variations percentage ratio after 300% of the 5th during 5 repeated stretchings.The result of sample of the present invention is b preferably W, 5Value is big to surpass 25%, more preferably no more than 20%.Hysteresis characteristic shows when the 5th stretches the ratio of unload forces and carrying capacity under 150% elongation.Tensile stress values be illustrated under the load to the drawing force of 150% elongation with when the 5th stretches to the ratio of the drawing force of 300% elongation.
Puu fiber of the present invention can be used for producing the elasticity textile product, for example woven, knitted fabrics and other textiless.
The following example explanation the present invention.
Prepare polyurethane elastomer as an example and measure its performance.
Embodiment 1:
From PolyTHF 1000 homopolymer with as the polyurethane elastomer of the TD I80/20 of main agents
PolyTHF 1000 homopolymer (BASF) of 510.29g (516.0mmol) devolatilization were reacted 50 minutes down at 88 ℃ with 58.92g (338.3mmol) TDI 80/20.After reaction terminating, recording the OH number is 37.0mg KOH/g (Mn=3033g/mol).The end capped prepolymer of this OH of 401.03g (132.3mmol) was reacted 50 minutes with 53.90g (215.4mmol) 4,4 '-MDI down at 88 ℃.After reaction terminating, NCO content is that the viscosity under 1.49% and 60 ℃ is 313000mPa*s.Be dissolved in N,N-dimethylacetamide with 23.5% solution the end capped prepolymer of this NCO and use the quadrol in N,N-dimethylacetamide to carry out chain extension, thus make with respect to the amine of titrating NCO content (0.36%) excessive for 2.22mmol NH ( 2)/kg polyurethane elastomer polymkeric substance.Owing to processing property and reproducibility reason, on film, measure the mechanical property of this polyurethane elastomer.For this reason, by on the sheet glass of the solution of prepared polyurethane elastomer being inclined to accurate horizontal aligument and make its under 50 ℃ in slow N 2In the air-flow dry 48 hours and make this solution film forming.Solution amount and concentration and plate area are mated mutually, to produce the thick film of 0.2-0.26mm.According to a) DIN 53504 (tension test) and b) DIN 53835 (hysteresis) these films are carried out mechanical test.Measuring result is summarized in the table 1.The trend of income value is basic consistent with the value of fiber.By the molar mass of gel permeation chromatography (GPC) mensuration gained polyurethane-urea elastomer, with the calibration of polymethylmethacrylate (PMMA) sample.
Embodiment 2:
From PolyTHF 1000 homopolymer, as the dimethyl terephthalate (DMT) of main agents and the polyurethane elastomer of chain termination amine
By improving temperature gradually and reducing pressure (finally to 240 ℃/7 millibars) PolyTHF 1000 homopolymer (BASF) of 508.33g (514.0mmol) devolatilization are reacted in the presence of the 20ppm tetra-butyl orthotitanate with 65.44g (337.0mmol) dimethyl terephthalate (DMT); Remove the methyl alcohol of formation by distillation.After reaction terminating, recording the OH number is 32.0mg KOH/g (Mn=3507g/mol).Make this material of 412.09g (117.5mmol) and 47.9g (191.4mmol) 4,4 '-MDI is 88 ℃ of down reactions 50 minutes, and the viscosity that obtains NCO content and be under 1.38% and 60 ℃ is the prepolymer of 166500mPa*s.Be used for preparing the end capped prepolymer of this NCO of 32.9g at 23.5 weight % solution of N,N-dimethylacetamide and use 288.2mg (4.710mmol) to be dissolved in 26.2gN, the amine mixt in the N-N,N-DIMETHYLACETAMIDE carries out chain extension.This amine mixt is formed (average molar mass 61.19g/mol, functionality 1.916) by 90 weight % quadrols and 10 weight % diethylamine.Excessive based on the amine of NCO content is 5.81mol%.Be similar to the performance test of the polyurethane elastomer that embodiment 1 so prepares.Measuring result is summarized in the table 1.
Embodiment 3:
From PolyTHF 1000 homopolymer with as the polyurethane elastomer of the dimethyl isophthalate of main agents
PolyTHF 1000 homopolymer (BASF) that make 452.05g (457.1mmol) devolatilization are as 2) under in the presence of the 20ppm tetra-butyl orthotitanate, react with 58.2g (299.8mmol) dimethyl isophthalate.The OH number that records the end capped prepolymer of this OH is 39.8mg KOH/g (Mn=2820g/mol).Make wherein 467.57g (165.8mmol) and 67.18g (268.4mmol) 4, it is the end capped prepolymer of NCO that 1.47% and 60 ℃ of following viscosity is 156300mPa*s that 4 '-MDI reacts 50 minutes formation NCO content down at 88 ℃.This material of 32.9g is diluted with the 107.1g N,N-dimethylacetamide.Add the solution of 296mg (4.93mmol) quadrol in the 25.9g N,N-dimethylacetamide as mentioned above.Be similar to the performance test of the polyurethane elastomer that embodiment 1 so prepares.Measuring result is summarized in the table 1.
Embodiment 4:
From PolyTHF 1000 homopolymer, as the dimethyl isophthalate of main agents and the polyurethane elastomer of chain termination amine
As described in embodiment 2, PolyTHF 1000 homopolymer (BASF) of 500.81g (506.4mmol) devolatilization are reacted in the presence of the 20ppm tetra-butyl orthotitanate with 64.47g (332.1mmol) dimethyl isophthalate.Gained OH number is 45.0mg KOH/g (Mn=2494g/mol).Make end capped prepolymer of this OH of 466.10g (186.9mmol) and 75.3g (300.9mmol) 4,4 '-MDI reaction obtains having the end capped prepolymer of NCO of 1.38% NCO content.Will be wherein 32.9g be dissolved in 107.1gN, be dissolved in quadrol in the 26.13g N,N-dimethylacetamide as mentioned above in the N-N,N-DIMETHYLACETAMIDE and with 340mg (5.56mmol) and the mixture of diethylamine mixes.Be similar to the performance test of the polyurethane elastomer that embodiment 1 so prepares.Measuring result is summarized in the table 1.
Embodiment 5:
From PolyTHF 650 homopolymer with as the polyurethane elastomer of the dimethyl isophthalate of main agents
PolyTHF 650 homopolymer (BASF) of 475.46g (738.3mmol) devolatilization are reacted with 110.75g (570.4mmol) dimethyl isophthalate under the catalysis of 20ppm tetra-butyl orthotitanate.OH number after the reaction terminating is 37.33mg KOH/g (Mn=3006g/mol).Make this prepolymer of 436.69g (145.3mmol) and 58.86g (235.2mmol) 4,4 '-MDI reaction.NCO content after the reaction terminating be 1.15% and the viscosity under 60 ℃ be 169 700mPa.s.Wherein 32.9g is dissolved in the 107.1g N,N-dimethylacetamide and mixes with the quadrol of 135.4mg (2.253mmol) in the 25.36g N,N-dimethylacetamide as mentioned above.Be similar to the performance test of the polyurethane elastomer that embodiment 1 so prepares.Measuring result is summarized in the table 1.
Embodiment 6:
From PolyTHF 650 homopolymer, as the dimethyl isophthalate of main agents and the polyurethane elastomer of chain terminator amine
32.9g is dissolved in the 107.1g N,N-dimethylacetamide from the end capped prepolymer of the NCO of embodiment 5.Add the quadrol that 300.9mg (4.917mmol) weight ratio the is 90:10-solution of diethylamine mixture in the 28.41g N,N-dimethylacetamide as mentioned above and carry out chain extension.Be similar to the performance test of the polyurethane elastomer that embodiment 1 so prepares.Measuring result is summarized in the table 1.
Comparative Examples:
Comparative Examples 1:
Polyurethane elastomer from 3-methyl-THF-THF multipolymer
1 hour 3-of devolatilization methyl-(PTG-L 3000 for the THF-THF multipolymer under 120 ℃/2 millibars to make 210.7g (72.24mmol), Hodogaya Chemical Company) with 29.44g (117.6mmol) 4,4 '-MDI reacted 80 minutes down at 88 ℃.Under 30 ℃ and nitrogen, the end capped prepolymer of this NCO of 32.90g is dissolved in the 107.10g N,N-dimethylacetamide fully.By this solution being mixed in 31 minutes with the quadrol of 374mg (6.22mmol) in the 107.1g N,N-dimethylacetamide 30 ℃ of following stirrings.Amino excessive value based on titrating NCO content in the solution is 4.00mol%.Be similar to the performance test of the polyurethane elastomer that embodiment 1 so prepares.Measuring result is summarized in the table 1.
Comparative Examples 2:
Polyurethane elastomer from PolyTHF 1800 homopolymer
Be similar to PolyTHF 1800 homopolymer (BASF) and 43.82g (175.1mmol) 4 that Comparative Examples 1 makes 196.18g (108.09mmol) devolatilization, 4 '-MDI reaction.Be dissolved in the 107.1g N,N-dimethylacetamide at 30 ℃ of 32.90g prepolymers that will so prepare down.With 63.33 weight % quadrols, 19.49 weight %1, the mixture of 2-propylene diamine and 17.18 weight % diethylamine is used for chain extension.Be dissolved in this amine mixt of 631mg in the 25.99g N,N-dimethylacetamide and under 30 ℃, in 31 minutes, add in this pre-polymer solution.Be similar to the performance test of the polyurethane elastomer that embodiment 1 so prepares.Measuring result is summarized in the table 1.
Figure A200780014803D00141
Figure A200780014803D00151
Table 1 shows that polyurethane elastomer produced according to the invention especially is better than conventional prior art polyurethane elastomer on required low elastic modulus (some application need), stress-strain behavior, hysteresis behavior and elastic recovery.In some cases, elastomerics of the present invention even surpass particularly advantageous value based on the polymkeric substance of the multipolymer of THF and 3-methyl-THF.

Claims (14)

1. method of producing polyurethane elastomeric fiber comprises:
A) make polymer diol form the end capped prepolymer of OH with it being reactive substance reaction,
B) make end capped prepolymer of described OH and di-isocyanate reaction form isocyanate-terminated prepolymer,
C) make described isocyanate-terminated prepolymer and chainextender, suitable words chain terminator and suitable other additive reactions of words form polyurethane elastomers and
D) described elastomerics spinning is formed fiber,
Wherein in described fiber, there are other polyurethane elastomers less than 15 weight %.
2. according to the process of claim 1 wherein described isocyanate-terminated prepolymer is further reacted in step c) with chain terminator.
3. according to the method for claim 2, wherein said chain terminator comprises primary amine, secondary amine, primary alconol or its mixture.
4. according to each method among the claim 1-3, wherein said polymer diol is that number-average molecular weight is the polytetrahydrofuran diol of 200-2500g/mol.
5. according to each method among the claim 1-4, wherein said glycol reactive materials is the derivative of vulcabond, diacid or diacid.
6. according to the method for claim 5, wherein said glycol reactive materials is the ester of terephthalic acid, m-phthalic acid and/or terephthalic acid and/or m-phthalic acid.
7. according to the method for claim 6, wherein said glycol reactive materials is m-phthalic acid or dimethyl isophthalate.
8. according to each method among the claim 1-7, the number-average molecular weight of the end capped prepolymer of wherein said OH is 500-5000g/mol.
9. according to each method among the claim 1-8, wherein the described vulcabond of step b) is 4,4 '-diphenylmethanediisocyanate or 2,4-or 2,6-tolylene diisocyanate.
10. according to each method among the claim 1-9, wherein said chainextender is a quadrol.
11., add before the spinning of wherein said other additives in step d) according to each method among the claim 1-10.
12. one kind by the elastomeric fibre that obtains according to each method among the claim 1-11.
13. the purposes of fiber in producing textiles according to claim 12.
14. the polyurethane elastomer that obtains is in the following way being produced according to the purposes in the elastomeric fibre of claim 12:
A) make polymer diol form the end capped prepolymer of OH with it being reactive substance reaction,
B) make end capped prepolymer of described OH and di-isocyanate reaction form isocyanate-terminated prepolymer,
C) make described isocyanate-terminated prepolymer and chainextender, suitable words chain terminator and suitable other additive reactions of words form polyurethane elastomers.
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